Refining tall oil



REFINING TALL OIL Filed March 17, 1942 3 Sheets-Sheet 1 C RUDE TALL OIL HEAT TREATM ENT WITH BORIC ACID AT REDUCED PRESSURE BORON-HEAT TREATED TALL OIL ADDITION OF GASOLINE- GASOLINE SOLUTION OF REMOVAL OF T A s BORON HLELABIEREATED ?\IOTAHEIN(EIS%D%FF COMPLEXES T EVAPORATION OF GASOLINE REFINED TALL plL REDUCED PRESSURE 'DISTILLATION RESIDUE I FURTHER REFINED TALL OIL FIG. I

. INVENTOR. JOSEPH N. BORGL IN BY ATTORNEY 1945" J. N. BORGLIN 2,374,975

' REFINING TALL OIL Filed March 17, 1942 s Shegts-Sheet 2 CRUDE TALL on. I

REDUCED PRESSURE DISTILLATION lN PRESENCE OF BORIC ACID RESIDUE OF REFINED BORON COMPLEXES TAL L OIL FIG. 2

3 INVENTOR. JOSEPH N. 80/? GL IN \QmM (s. mam, AlT RNE 1945. J. N. BORGLIN 2,374,975

REFINING TALL OIL Filed March 17, 1942 s Sheets-Sheet is CRUDE TALL OIL ADDITION OF GASOLINE GASOLINE SOLUTION OF TALL OlL HEAT TREATMENT lN PRESENCE OF BORIC ACID GASOLINE SOLUTI N OF BORON- HEAT TR ATED TALL OIL COOLING REMOVAL OF A PRECIPITATED BORON COMPLEXES GASOLINE SOLUTION OF REFINED TALL OIL EVAPORATION OF v GASOLINE REFINED TALL OIL FIG.3 I

INVENTOR. J OSERH N. BORGL /N ATTOR NEY liquor. This black liquor contains the non-celluof solvent extraction or distillation or both as crude tall oil soap is characterized as being dark, treated by subjecting the refined tall oil to a mercaptans, and higher alcohols. prises subjecting the tall oil to a reduced pressure Patented Mayl, 1945 T UNITED- STATES PATENT OFFICE Joseph N. lion-31in, assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware Application March 17, 1942, Serial No. 435,045

This invention relates to the refining of crude tillation operation. Reduced pressure ,dis atall oil and, more particularly, to the use of boron tion of the tall oil in the presence of a mu compounds as a crude tall q il refining agent. compound, or the heating of a solvent solution In the manufacture of paper pulp, the wood of tall oil in the presence of a boron compound chips which form the basis of the pulp are acted followed by cooling and subsequent separation of v i on by an alkaline liquor which attacks the nonthe phases will also effect separation. cellulose constituents as, for example, fatty and More specifically, the refining of the tall oil resin acids, and leeches them from the cellulose. in-accordance with the process of this invention The fresh alkaline liquor which is used in this 4 is carried out by first heating the tall oil in the so-called cooking operation is known as the white presence of a suitable boron compound at atmosliquor and the spent liquor 'of digestion which pheric orreduced pressure, This boron treated is drained from the pulp is known as the black tall oil solution may then be refined by means loseconstituents of wood, the major portion of diagrammatically shown in Fig. I. The boron which is made p of the resin and fatty acids in is treated tall oil may be dissolved in any suitable the form of the sodium soap. Upon, cooling of solvent which causes the precipitation of insoluthe black liquor, the soaps separate and float on ble matter and a boron compound impurity. the top of the liquor due to the salting out action Afterremoval of the precipitated materials, the of the strong alkali. This floating matter is solvent may be evaporated to recover the refined known in the trade as crude talloil soap. This tall oil. This refined tall oil may be further brown, mpure, d hi y ill-Sm llin Upon reduced pressure distillation operation.

atm nt of the soap with an acid a less dark 7 When the refining of the boron treated tall 011 brown, viscous, oily product is obtained and" is made by means of reduced pressure distillaknown in the trade as tall oil. as tion, the operation may be either regular, flash,

Within limits reported in the literature, tall batchor continuous. The distillation permitsreoil contains to 60% fatty acids, mainly of covery of a distillate rich in fatty'and resin acids, the oleic series, 25% to 60% resin acids, which and a residue containing the boron compound may include 50% to 90% abietic acids, and 7% complexes. v to 20% unsaponifiable material. This unsaponigo The crude tall oil may be treated in the man-' fiable material may contain phytosterol, lignin, ner diagrammatically shown in Fig. 2 which com- The removal of latent and visible color bodies distillation operation at a temperature of about and odor producing compounds of the tall oil 250 C. in the presence of a suitable boron com-; is desirable commercially but has always been pound, whereupon a distillate is obtained rich in a difficult problem. The exact constitution or fatty and resin acids and a residue containing a nature of these visible color bodies is unknown. boron compound complex. 1 Invisible or latent color bodies develop color The crude tall oil may also be treated in the when the tall oil is subjected to certain treatmanner diagrammatically shown in Fig. 3 which ment, for example, saponification. The visible 40 comprises dissolving the tall oil first in a suitable color bodies can be largely removed by ordinary .solvent and then heating the solvent solution of reduced pressure distillation. This procedure, tall oil in thepresence of the boron compound. however. does not remove the latent color bodies Cooling of this heated solution of boron treated nor does it yield as light a colored product as tall oil causes the boron compound impurities may be desired. Further disadvantages of the to precipitate which'may be m v y adistillation method are the occurrence of equiption. The clear solvent solution of tall oil is then ment corrosion which occurs during the distillasubjected to a distillation operation to remove the tion process, and partial destruction of the relasolvent and permit recovery of the refined tall oil.

tively commercially valuable fatty and resin acid The method in accordance with this invention components. H is illustrated by the following specific examples:

In accordance with this invention, tall oil may Emu 1 be refined by treating the tall oil with a boron compound and thereafter separating the boron /Bo? mkmsmlatmn treatment complexes leaving refined tall oil. The separation 2 r dark dl d n n grading D on the is acc pli h d after eat n with & r n mrosin color scale was distilled under a reduced ro n by subjecting the boron treated tall oil pressure'of 10mm. of mercury in the presence of to eit r a ven en r ction Operation. or a dis- 2 g. of boric acid at a maximum temperature of 300 C. The distillate and residue obtained from this operation analyzed as follows:

Residue Distillate Fatty acid.

EXAMPLE 2 Sodium tetrabrate-Flash distillation treatment 300 g. of dark colored tall oil grading D on the rosin color scale was heated at 150 C. for 15 minutes with 3 g. of sodium tetraborate. The treated tall oil was then subjected to a flash distillation operation at a reduced pressure of 5 mm. of mercury at a temperature of 275 C. whereby 225 g. of distilled product was obtained. This product graded W on the rosin color scale and yielded soaps upon saponification having superior color.

EXAMPLE 3 Boric acid-Solvent extraction treatment 300 g. of dark colored tall oilgrading Don the rosin color scale was heated at 150 C. for 15 minutes with 3 g. of boric acid. To this boron treated tall oil mixture was added 1500 g. of gasoline and the mixture agitated at 25 C. -The gasoline phase of tall oil separated from the precipi tated insoluble matter and the boron compound impurities. Evaporation of the gasoline by means of distillation resulted in 250 g. of refined tall oil having a color of H on the rosin color scale. 100 g. of this refined tall oil was further refined by means of distillation at a reduced pres-' sure of 5 millimeters of mercury at a maximum bath temperature of 275 C. whereupon 85 g. of distillate was recovered which graded X on the rosin color scale.

EXAMPLE 4 Boric anhydride-S0lvent extraction treatment 300 g. of dark colored tall oil grading D on the rosin color scale was dissolved in 1500 g. of gasoline and then heated at a maximum temperature of 125 C. for a period of 24 hour in the presence of 15 g. of boric anhydride. During this boric anhydride heating treatment, the mixture was thoroughly agitated.- The mixture was cooled to 25 C. with agitation, whereupon the boric anfhydride complex impurities precipitated and left a'clear gasoline solution of refined tall oil which was then separated from the precipitate and subjected to a distillation operation to remove the asoline. 260 g. of the refined tall oil was recovered having a color grade of H on the rosin'color scale.

The methods utilized in carrying out the processes of this invention may involve reacting the crud'e tall'oil itself or a solvent solution of the crude tall oil with a suitable boron compound.

The reaction with crude tall oil itself may be brought about by heating the tall oil in the presence of a boron compound at a temperature from about 100 C. to about 300 C. and preferably from about 125 C. to about 175C. -at atmosphericpressure or at a reduced pressure.

rlod or time of from about 1 minute to about hours and preferably from about 5 minutes to about 2 hours. The amount -of boron compound 5 tall oil are boric acid, sodium used may be from about 0.1% to about 10% and preferably from about 0.2% to about 5%.

- Suitable boron compounds which have been found to exert a desirable refining action on the tetraborate, commonly referred to as borax, boric anhydride, etc.

The boron treated tall oil mixture may be refined to remove the boron complexes by means of solvent-extraction which comprises dissolving the boron treated tall oil mixture in a suitable solvent as, for example, gasoline, toluene, petroleum ether, etc., at a temperature of about 0 C. to about 150 C. and preferably at a temperature of about 20 C. to about 40 tion of the boron treated tall oil causes insolubles as, for example; the boroncompound impurities to be precipitated from the mixture whereupon the solvent solution of tall oil is separated from the precipitated impurities and treated in any suitable manner as, by distillation to removethe solvent. Further treatment of this refined tall oil may be made by subjecting the refined tall oil to a reduced pressure distillation operation whereby still further refined tall oil distillate may be recovered.

The boron treated tall oil mixture may also be refined by subjecting the mixtureto a reduced pressure distillation whereby the boron compound complexes which are of a low vapor pressure remain behind and the refined tall oil is distilled off. Distillation may be carried out as a continuous process, a batch process or a flash process. .This reduced pressure distillation may be carried out at pressures of 1 mm. to 50 mm. of mercury and preferably less than 20 mm. of mercury. The bath or pot temperature of the distillation may be about 200 C. to about 300 C. and, if desired, the distillation may be carried out in the presence or absence of inert gas.

The tall oil may also be refined by subjecting the tall oil to a distillation operation at a reduced pressure in the presence of a suitable boron compound (Fig. 2). The distillation operation may be carried out under the conditions set forth with respect to distillation refining-treatment of the boron treated tall oil hereinabove described.

A further modification for the refining of tail oil (Fig. 3) comprisesdissolving the tall oil to be refined in any suitable solvent as, for example, gasoline, petroleum ether, toluene, etc., which solvent solution of tall 011' is then heated with a boron compound. During the heating process which may be carried out at a temperature of about C. to about 200 C. and preferably at a temperature of about C. to about C., the boron tall oil mixture is constantly agitated, whereby boron compound impurity complex precipitates. Precipitation of the boron compound impurity complex may be facilitated by cooling the mixture, after which the clear solution of solvent tall oil may be withdrawn from the boron compound impurities in any suitable manner as heating operation may be carried out over a peby decantation, filtration, or centrifuging, and

the solvent evaporated from the refined tall oil in any suitable manner as by means of distillation. The refined tall oil may be further refined by subjecting the tall oii-to a reduced pressure distillation operation.

The products obtained .in accordance with the distillation methods of this invention are the distillate and the distillation residue. The distillate, which is a limpid liquid and rich in fatty and resin acids, may be saponified for use in soap, disinfectant. emulsifying agent, etc.; If desired, the distillate or refined product obtained in ac- C. This solvent soluacids.

- Patent is:

compound capable of removing the visible or latent color bodies of said tall 011 and subjecting the treated tall oil to a distillation operation.

point, they may be used as resin and saponified for use as emulsifying agent as, for example, in asphalt.

Further refining of the refined tall oil may be made by treatment with a suitable solid adsorbent as, for example, activated carbon, activated alumina, synthetic aluminum and magnesium silicate, fullers earth, adsorbent clay, activated silica, activated bone black, silica fiour, synthetic magnesium silicates, etc.

Treatment of the refined tall oil with any one v of the above mentioned adsorbents consists in suspending or agitating the adsorbent in the refined tall 011 or solution thereof and then separating the adsorbent with the further adsorbed color bodies from the tall oil solution, or it may consist in passing the refined tall oil in liquid phase through a mass of the adsorbent. The latter type of treatment is convenient as it combines contacting and separating at a single operation. This additional refining of the refined tall oil with any one of the above mentioned suitable adsorbents will preferably be given at a temperature of about C. and may be given at a temperature between about 0 C. and about The theory involved in accordance with this invention is not definitely known; however, it appears that the boron compounds form a complex with the latent and visual color bodies present in the tall oil to be refined. Thus, heating of the tall oil in the presence of a suitable boron compound probably causes the formation of a boron impurity complex which is of low vapor pressure and therefore the higher vapor pres- 2. The method of refining tall oil which includes heating tall oil in the presence of a boron compound capable of removing the visible or latent color bodies of said tall oil, and subjecting the treated tall oil to a reduced pressure distillation operation.

3. The method of refining tall oil which includes heating tall 011 in the presence of a boron compound capable of removing the visible or latent color bodies of said tall oil, subjecting the treated tall oil to a solvent extraction operation, and recovering the refined-tall 011.

J 4. The method of refining tall oil which includes heating tall oil in the presence of a boron compound capable of removing the visible or latent color bodies of said tall oil, subjecting the treated tall oil to a solvent extraction operation, removal-of the tall 011 from the solvent. and subjecting the removed tall oil to a reduced pressure distillation operation.

5. The method of refining tall oil which includes the step of subjecting the tall oil to a reduced pressure distillation operation in the presence of a boron compound capable of removins the visible or latent color bodies of said tall 011. v i

- 6. The method of refining tall oil which includes the stepof heating a solvent solution of tall 011 in the presence of a boron compound capable of removing the visible or latent color bodiesof said tall oil, and recovering the tall oil.

7. The method of refining crude tall 011 which includes heating tall 011 in the presence of boric acid, subjecting the treated tall oil to a solvent includes heating tall oil sure constituents as, for example, thefattyxand resin acid components of, the tall oil may be re moved from the boron impurity complexes by means of distillation. The boron impurity complexes are also of a decreased solubility, particularly in petroleum hydrocarbons which permit a further method of refining the tall oil as by solvent extraction, wherein the more soluble fatty and resin acids'are separated from the nonsoluble, boron impurity complexes.

In accordance with the methods of this invention, either the crude tall oil soap or the tall oil may be refined. Where crude tall oil soap is used as the raw material, treatment with any suitable mineral acid as, for example, sulfuric acid, or hydrochloric acid prior to refining, is used to reduce the soap mixture to the free. fatty and resin W'here tall rial. this mineral acid treatment is not ncessary:

In accordance with this invention, the use of boron compounds provides an eiiicient means whereby the latent as well as visual color bodies in tall oil can be removed. 4

' The odor of the tall oil is considerably improved by the above treatment.

oil is used as the raw matewhatlclaimanddesiretoprotectbylietters '1. The method of inthepreseneeoia'borcn includes heating the sure between about 1 7 mercury.

extraction operation, and recovering the refined tall oil.

8. The method of refining crude tall 011 which includes heating tall oil in the presence of borax.

9. The method of refining crude tall oil which in the presence of boric anhydride, subjecting the treated tall 011 to a solventextraction operation, and recovering the refined tall oil.

10. The method of refining crude tall oil which tall oil in the presence of a boron compo visible or latent color bodies of said tall oil at a temperature of about O. to about C. for a period of about 5 minutes toabout 2 hours.

subjecting the treated tall oil .to' as petroleum hydrocarbon solvent extraction operation, and

recovering the refined 11. The method of includes the step 01' tall oil. refining crude tall oil which subjecting the tall oil to a distillation operation at a reduced pressure of a less than 20 mm. of

mercury and at a temperature of about200' C. to about 300 C. in the presence of a boron compound capable-oi removing the visible tali oil.

12. The method of cludes heating tall oil or latent colorbodies of said in the. presence ofa boron compound capable of removing the visible or' latent g color bodies of said tall oiL iina subjectthe treated tail oil to distillationat arresmm. and about 50 mm. or

und capableof removing the r r flnins an oil wh ch in- 

